Fabrication-friendly polarization-sensitive plasmonic grating for optimal surface-enhanced Raman spectroscopy

Plasmonic nanostructures are widely utilized in surface-enhanced Raman spectroscopy (SERS) from ultraviolet to near-infrared applications. Periodic nanoplasmonic systems such as plasmonic gratings are of great interest as SERS-active substrates due to their strong polarization dependence and ease of fabrication. In this work, we modelled a silver grating that manifests a subradiant plasmonic resonance as a dip in its reflectivity with significant near-field enhancement only for transverse-magnetic (TM) polarization of light. We investigated the role of its fill factor, commonly defined as a ratio between the width of the grating groove and the grating period, on the SERS enhancement. We designed multiple gratings having different fill factors using finite-difference time-domain (FDTD) simulations to incorporate different degrees of spectral detunings in their reflection dips from our Raman excitation (488 nm). Our numerical studies suggested that by tuning the spectral position of the optical resonance of the grating, via modifying their fill factor, we could optimize the achievable SERS enhancement. Moreover, by changing the polarization of the excitation light from transverse-magnetic to transverse-electric, we can disable the optical resonance of the gratings resulting in negligible SERS performance. To verify this, we fabricated and optically characterized the modelled gratings and ensured the presence of the desired detunings in their optical responses. Our Raman analysis on riboflavin confirmed that the higher overlap between the grating resonance and the intended Raman excitation yields stronger Raman enhancement only for TM polarized light. Our findings provide insight on the development of fabrication-friendly plasmonic gratings for optimal intensification of the Raman signal with an extra degree of control through the polarization of the excitation light. This feature enables studying Raman signal of exactly the same molecules with and without electromagnetic SERS enhancements, just by changing the polarization of the excitation, and thereby permits detailed studies on the selection rules and the chemical enhancements possibly involved in SERS.peerReviewe

High Aspect-Ratio Iridium-Coated Nanopillars for Highly Reproducible Surface-Enhanced Raman Scattering (SERS)

A variety of different gold and silver nanostructures have been proposed over the years as high sensitivity surface-enhanced Raman scattering (SERS) sensors. However, efficient use of SERS has been hindered by the difficulty of realizing SERS substrates that provide reproducible SERS response over the whole active area. Here, we show that atomic layer deposition (ALD) grown iridium can be used to produce highly reliable SERS substrates. The substrates are based on a periodic array of high aspect-ratio iridium coated nanopillars that feature efficient and symmetrically distributed hot spots within the interpillar gaps (gap width < 10 nm). We show that the enhancement with the iridium based nanostructures is of significant magnitude and it equals the enhancement of silver based reference substrates. Most notably, we demonstrate that the ordered and well-defined plasmonic nanopillars offer a measurement-to-measurement variability of 5%, which paves the way for truly quantitative SERS measurements